Supported-catalyst and use of same

ABSTRACT

The invention concerns a supported catalyst in the form of packing and constructed on an open-pore support material on whose external and internal surfaces a macro-porous ion exchange resin is mechanically and/or chemically affixed.

The invention concerns a supported catalyst and use of same.

The development of new supported catalyst containing sulphonic acidgroups on a polymer frame, is of great importance for a number ofindustrial chemical processes, for example the production of certainethers from the reaction of C₄ or C₅ fractions of the refinerytechnology with methanol or ethanol as admix components for theproduction of fuel (cf. Hydrocarbon Processing, November 1990, pp.126,128).

To produce improved, particularly more environmentally friendlyanti-knock petrol qualities, methyl tertiary butylene ether (MTBE) andtertiary amyl methyl ether (TAME) or tertiary butylene ethylether (ETBE)are particularly important admix components.

The processes to produce these components are generally carried out asreaction distillation processes or processes to treat and/or react theproducts by catalytic distillation.

In case of catalytic distillation the reaction and the processing of thereaction mixture by distillation and/or rectification, which usuallytakes place in a following step of the process, are carried out in onesingle reaction apparatus only, which also includes the processing part.

In this connection the introduction and affixing of the catalyst in thereaction apparatus represents a special problem. Usually in the case ofsolid or supported catalysts a filling of the catalyst into one orseveral superposed solid beds, permeated by the reaction mixture, isprovided.

When the macro-porous cross-linked polystyrene sulphonic acid, used inthe industrial production of the MTBE or TAME, is used in spherical formas loose filling in a solid bed as catalyst in the reaction of methanoland butylene, disadvantages like higher resistance to flow, edge flow aswell as the wear of the catalyst are involved.

To avoid these disadvantages in a process to carry out chemicalreactions in a reaction-distillation apparatus it has been proposed toaccommodate the catalyst consisting of macro-porous cross-linked gelpellets of a polystyrene sulphonic acid in closed pouches, which areconstructed from and retained by a wire netting and are assigned to asolid bed made to suit the reaction apparatus by coiling in the form ofa spiral, cf. EP-A-0 466 954.

It has been further proposed for the purpose of improving the materialexchange properties of the solid bed catalyst packing to construct thecatalyst in the shape of exchange bodies like Raschig rings, for whichpurpose a mixture of cross-linked styrene divinyl benzene copolymer inground form is coextruded with the thermoplastic polypropylene to suchan exchange shape and is sulphonated afterwards, cf. FR-A-2 297 083.

This concept has been further developed inasmuch the formed bodies wereproduced directly from macro-porous ion exchange resins without the useof a thermoplastic material, cf. DE-A-3 930 515. The formed bodiesobtained by this method have the expected good material exchangeproperties as well as a good catalytic activity. It is, however, noteasy to manufacture these in production quantities and they leave a lotto be desired regarding their mechanical strength.

From U.S. Pat. No. 4,250,052 supported catalysts are known in the formof a packing, which can be coated with a polymer made of vinyl aromaticmonomers and can be subsequently sulphonated. For this purpose thepolymer is dissolved, applied to the support and the solvent is thenremoved again. A disadvantage of this process and/or of the catalystproduced in this manner is that the polymers mentioned cannot bestrongly cross-linked as otherwise they could not be dissolved. Theresult of this is that they can be corroded, separated or dissolved bythe reaction mixture also. In addition, in the manner mentioned, nomacro-porosity for the polymer can be achieved.

The object of the invention is to produce a supported catalyst withmaterial exchange properties which can be also produced in productionquantities.

This objective is achieved by supported catalysts according to theclaims 1 to 14 as well as by a process to carry out chemical reactionsby using these supported catalysts according to claims 15 to 24.

The supported catalysts according to the invention in the form ofpacking are constructed from a basic body consisting of open poroussupport material, on the external and internal surface of which amacro-porous ion exchange resin is affixed mechanically and/orchemically.

A chemical affixing may be preferred and is obtained, for example bysilanising the surface of the open-porous support material withsubsequent polymerisation build-up.

The packing of the supported catalyst is constructed as Raschig rings,Berl saddles, torus saddles, packing rings with web or cross web, Pallrings, other hollow bodies, hollow spheres, ordered packages, honeycombbodies and the like with a proportion of the hollow space of themacro-porous ion exchange resin being 5 to 95%.

The support material of the aforementioned supported catalyst consistsof open-pore glass, sintered glass, open-pore ceramic material onaluminium silicate base, sintered glass ceramics, foam ceramics,activated carbon or activated coke.

In the case of sintered glass or sintered glass ceramics the surfacearea can be increased by a prior treatment with aqueous alkali hydroxidesolution. By this the number of silanol groups on the surface will beincreased on the one hand, which surface is then accessible forsilanisation and by the etching process a rougher surface is created onthe other, thereby favouring a mechanical affixing on the polymerapplied.

While glass with open pores, sintered glass, sintered glass ceramics orceramic material with open pores are commercially available already in abasic or packing form suitable for material exchange purposes, activatedcarbon or activated coke with suitable pore sizes can be used accordingto the invention for catalyst beds. Suitable pore sizes are obtainedfrom bulk material after a selection process from suitable sievedmaterial in selected size ranges.

The macro-porous ion exchange resin on and in the support material ispreferably a macro-porous cross-linked polystyrene sulphonic acid,whereby a different degree of cross-linking can be accomplished tocorrespond with the requirements by using greater or lesser amounts ofdivinyl, benzene or diisopropenyl benzene. The polymer is preferablycross-linked to such a high degree, that it cannot be dissolved by thereaction mixture of the reaction to be catalysed.

The ion exchange resin can be applied to the support material by twodifferent processes.

In case of the so called impregnating polymerising process the formedbodies are impregnated with the reaction mixture, the excessimpregnating solution is removed and subsequently the polymerisation iscarried out.

In case of the precipitating polymerising process the packing is inexcess in the reaction mixture during the polymerisation. The advantagesof the precipitation polymerising process are a very uniformdistribution of the polymer in the pores of the support material, inaddition a high porosity, since the solvent can act as a pore former, aswell as the simple production manner, since no steps are required toeven out the distribution of the monomers on the support.

An additional advantage is that the polymer content in the completed ionexchange resin can be set simply by the ratio of a suitable solvent tothe monomer mixture and that the polymer, when using the appropriatesolvent, is already in the swollen form so that possible damage of thesupport material by the swelling process can be avoided to a greatextent. Methanol or i-octane, as well as pentadecane may be used assolvents. A C₁₄ - to C₁₇ -n-paraffin fraction can also be used.

By the process mentioned a macro-porous polymer is produced in the poresand on the surface of porous packing, which will subsequently receiveion exchange properties by sulphonation.

In case of the precipitating polymerisation process the polymerisationis carried out depending on the concentration of the original materialsstyrene and divinyl benzene or disopropyl benzene in the pore former orof the solvent in the pores of the packing up to that degree ofpolymerisation, at which the formed polymer in flaky form becomesinsoluble in the pore former and/or the solvent and precipitates. Thepolymer flakes produced in this manner in the pores of the supportmaterial can be affixed in the pores of the support material purelymechanically and are protected from mechanical damages by thesurrounding support material.

For certain reactions it is useful to treat supported catalysts of thetype described above with Group7 or Group 8 metals of the periodictable, particularly with palladium, platinum, ruthenium or rhodium inquantities of 0.1 to 100 g/kg of the ion exchange resin.

As has already been indicated, the polymer can be additionally affixedchemically on the support material. A suitable chemical coupler is usedfor this purpose. For example silanes are suitable couplers for allformed bodies which have OH groups on their surfaces.

If the polymer to be coupled has a vinylic monomer base, vinyl-groupcarrying silanes are preferred as couplers, particularly phenyl-vinyldiethoxysilane, phenyl-methyl vinyl silane, triethoxy-vinyl silane ortrichlor-vinyl silane.

The supported catalyst can be produced by impregnating the packing with0.1 to 60% by weight with a mixture consisting of 10 to 80, preferably30 to 70% by weight of styrene, 2 to 25, preferably 5 to 10% by weightof divinyl benzene, 1 to 88, preferably 20 to 50% by weight of a poreformer or of a solvent as well as an effective quantity of apolymerisation initiator; carrying out the polymerisation reaction undera temperature increase of 30° to 90° C.; and subsequently treating thepolymer material affixed in the pores of the packing with a sulphonatingacid. In this case the proportion by weight of the pore former or of thesolvent is selected so that the proportion by weight of the mixture ofstyrene and divinyl benzene adds up to 100% by weight.

A supported catalyst produced according to the precipitatingpolymerisation process can be obtained by adding a mixture of 10 to 80,preferably 20 to 50% by weight of styrene, 2 to 25, preferably 5 to 10%by weight of divinyl benzene, 1 to 88, preferably 20 to 50% by weight ofa pore former or solvent as well as an effective quantity of apolymerisation initiator on the one hand and a C₁₄ - to C₁₇ -n-paraffinfraction on the other in a weight ratio of 10 to 1 to 1 to 10, to 5 to50% by weight of the support material, based on the total mixture,conditioning it under vacuum, polymerising, washing out the excess poreformer and externally adhering polymer gel, followed by sulphonating.

As pore formers C₆ - to C₁₆ -alkanes, e.g. n-heptane, pentadecane,i-octane as well as C₉ - to C₁₃ -fractions of the n-paraffin productioncan be used. These pore formers have good solubility for the styrene anddivinyl benzene monomers used for the production of the ion exchangeresin, but only a slight swelling ability for the polymer produced (cf.Catalytic Chemistry, Bruce C. Gates, John Wiley & Sons, 1992, p.221).

In this manner a solid phase, consisting preferably of microspheres, isformed in the hollow spaces of the support and on the support material,and the volume originally occupied by the solvent for the monomersremains as macro-pores after the removal of the solvent, which passthrough the entire cross-linked polystyrene and thus enable a goodaccess of the reacting materials for the intended chemical reactionsafter sulphonation. At the same time an increase of the active surfacecan be achieved by this.

This is why in a preferred embodiment the pore formers can be alsosolvents for the monomer mixture in case of the precipitationpolymerisation. In case of the precipitation polymerisation loweralkanols like methanol are also suitable as solvent. Combinations ofsolvent and pore former can also be used.

The sulphonating acid may be an aromatic or an aliphatic sulphonic acid,chlorosulphonic acid or sulphuric acid. Furthermore, sulphur dioxide aswell as sulphur dioxide addition compounds like that of dioxane,dimethyl aniline or pyridine are suitable.

Sulphuric acid is less preferable, as the concentration necessary oradequate sulphonation has a noticeable oxidizing affect and may lead tothe disintegration of the polymer frame.

Preferred aromatic sulphonic acids are benzene sulphonic acids andpreferred aliphatic sulphonic acids are methyl sulphonic acids.

In a further preferred embodiment the acids may also contain solventslike chloroform, nitromethane or acetonitrile.

The supported catalysts according to the invention are generally used tocarry out the chemical reactions of etherification, esterification,hydrogenation, alkylisation, hydration, dimerisation, oligomerisation orcombination of these as well as the respective reverse reactions.

Particularly preferred is the carrying out of one of the above mentionedchemical reactions with simultaneously applied separating operation likeadsorption, absorption, extraction, stripping, distillation,rectification, fractionating, membrane process or the like to separatethe required products. In this case the counter-current of the gaseousor liquid phase is suitable for a single or multiple phase gaseous andliquid reaction, since the supported catalysts according to theinvention have a high degree of spacing and thus cause a low pressureloss.

A preferred chemical reaction for using the supported catalyst accordingto the invention is the chemical reaction of etherification and theseparation of the reaction products by reactive distillation to obtaintertiary alkyl ethers from the reaction of alkanoles with alkenes; suchas to obtain MTBE from the reaction of methanol with i-butylene; toobtain i-propyl-tertiary butylether (PTBE) from the reaction ofi-propanol with i-butylene; to obtain ETBE from the reaction ofi-butylene with ethanol; or to obtain TAME from the reaction ofi-pentene-(1) or i-pentene-(2) with methanol. Further preferredreactions are the production of i-propanol from the reaction ofpropylene with water and the production of tertiary butyl alcohol (TBA)by reacting i-butylene with water.

This present invention is explained in detail based on the followingexamples as well as the results contained in Tables 1 and 2 and theFIGS. 1 and 2.

EXAMPLE 1

As support material formed bodies made of open-porous sintered glass inthe form of Raschig rings with the dimensions 8.8 mm:9 mm (outsidediameter×height).

This support material is characterised by a surface of up to 0.4 m² /gand a pore volume of up to 70%. The pore diameter can be varied from 1.6μm to 400 μm, the temperature resistance is up to 450° C.

40 pieces of the aforementioned rings have a mass of 12.5 g and wereimpregnated with a mixture of 22.7 g stryene, 13.7 g pentadecane, 2.9 gdivinyl benzene and 50 mg azoisobutyronitrile. The impregnation solutionnot accommodated in the pores was removed. The impregnated rings wereplaced into a sealed, pressurised metal container and were polymerisedat a temperature of approx. 75° C. in a heating cabinet for the periodof 10 h. The pressurized container is necessary to prevent the changingof the monomer mixture during the polymerisation by vapourisationprocesses. The polymer content of the rings treated in this manner wasapprox. 20 to 25% by weight. The rings were cooled afterwards to roomtemperature and subjected to sulphonation. 500 mL of the formed bodiesobtained were covered completely with chloroform and made to react with50 mL of chlorosulphonic acid for 20 h while excluding moisture.Subsequently the reaction solution was poured slowly on ice, the formedbodies were rinsed with chloroform and rinsed with methanol anddeionised water to completely remove the sulphonating agent and acid.The formed bodies were stored in water.

EXAMPLE 2

12.5 g of the support material described in Example 1 was added to amixture with the weight ratio of 1 to 1 of 22.7 g styrene, 2.9 g divinylbenzene, 13.8 g i-octane, 0.05 g azoisobutyronitrile on the one hand andC₁₄ - to C₁₇ -n-paraffin fraction on the other, so that the formedbodies to be impregnated were fully covered. Afterwards the mixture wasconditioned for 2 min under vacuum to fill all the pores. The mixturewas subsequently heated for 16 h at 60° C.

The polymer gel surrounding the formed bodies as well as the pore formerwere washed out after the completion of the reaction with chloroform.The formed bodies produced thus contained approx. 10% by weight polymer.

By repeating the treatment according to this method the polymer contentcan be increased to approx. 20% by weight.

500 mL of the formed bodies obtained were fully covered with chloroformand made to react with 50 mL chlorosulphonic acid for 20 h whileexcluding moisture. Subsequently the reaction solution was poured slowlyon ice, the formed bodies were rinsed with chloroform and rinsed withmethanol and deionised water to completely remove the sulphonating agentand acid. The formed bodies were stored in water.

The abbreviations used in Table 1 have the following meanings:

Cap: Capacity of the catalyst used

n_(i) : Hole flow of the component i

T: Dwell time

X_(i) : Conversion of the component i

Y_(i) : Yield of MTBE based on the component i

Component i: MeOH or IB

MeOH: Methanol

IB: i-butylene

sSDCmT: Sulphonated styrene/divinyl-benzene copolymer, macro-porous,produced by impregnating polymerisation

sSDCmF: Sulphonated styrene/divinyl-benzene copolymer, macro-porous,produced by precipitating polymerisation

sSDC: Sulphonated styrene/divinyl copolymer

MPI: Macro-porous ion exchange rings

Table 2 shows the effective reaction speeds of the MTBE formation. Theyare based on the capacity of the catalyst on the one hand, on the masson the other, and finally on the bulk volume of the dry catalyst.

The bulk density of the dry catalyst was established by weighing themass which takes up a given bulk volume, or by measuring the volume of agiven mass. In the present case a volume has been assumed.

                  TABLE 1                                                         ______________________________________                                        Experimental settings of the catalysts used                                   The pressure and temperature have been held constant in all                   experiments (p = 20 × 10.sup.5 Pa; T = 65° C.)                   ______________________________________                                                         Cap     Weight                                                                              n.sub.MeOH                                                                            n.sub.IB                               Experiment                                                                            Catalyst (meg/g) (mg)  (mmol/min)                                                                            (mmol/min.)                            ______________________________________                                        1       sSDCmT   0.506   1886  30      28.57                                  2       sSDC     0.419   1804  30      28.57                                  3       MPI      4.63    1500  30      28.57                                  4       A15      4.75    1928  30      28.57                                  5       SPC118   4.40    1932  30      28.57                                  6       sSDCmF   0.595   2011  30      28.57                                  ______________________________________                                                                 Conversion                                                                    X (%)     Yield Y (%)                                Experiment                                                                            Catalyst t(min)  X.sub.MeOH                                                                           X.sub.IB                                                                           Y.sub.MeOH                                                                           Y.sub.IB                          ______________________________________                                        1       sSDCmT   25.18   2.7    2.8  2.7    2.8                               2       sSDC     25.18   0.33   0.35 0.33   0.35                              3       MPI      25.18   1.85   1.95 1.86   1.96                              4       A15      25.18   7.00   7.3  7.0    7.3                               5       SPC118   25.18   7.5    7.9  7.5    7.9                               6       sSDCmF   25.18   0.54   0.57 0.51   0.57                              ______________________________________                                    

                                      TABLE 2                                     __________________________________________________________________________    Results of the Catalysts used                                                                Rate e.sub.eff                                                                       Rate m.sub.eff                                                                         Rate V.sub.eff                                            P   (MTBE) (MTBE)   (MTBE)                                         Experiment                                                                          Catalyst                                                                            g/mL!                                                                             mmol/(s eq)!                                                                         mmol/(s g)! × 10.sup.3                                                           mmol/(s mL)! × 10.sup.3                 __________________________________________________________________________    1     sSDCmT                                                                             0.328                                                                             14.1   7.13     2.34                                           2     sSDC 0.328                                                                             2.24   0.94     0.31                                           3     MPI  0.384                                                                             1.34   6.20     2.38                                           4     A15  0.577                                                                             3.82   18.14    10.46                                          5     SPC118                                                                             0.506                                                                             4.43   19.49    9.86                                           6     sSDCmF                                                                             0.328                                                                             2.27   1.35     0.44                                           __________________________________________________________________________     Rate Z.sub.eff, MTBE: Reaction speed or the MTBE formation                    if Z = e: Based on the equivalent of the resin used                           if Z = m: Based on the mass of the resin used                                 if Z = V: Base on the bulk volume of the resin used                      

The catalyst of Experiment 1 was produced according to Example 1.

The catalyst of Experiment 2 was produced in an analogous manner, butwithout pore former and thus is not macro-porous. This catalyst isobviously poorer in the test reaction of the MTBE formation than that ofExperiment 1.

The catalyst of experiment 6 was produced according to Example 2.Although as far as activity is concerned it is situated below that ofthe catalyst of Experiment 1, its production, however, is less costly.Experiments 3 to 5 are comparison experiments with standard ionexchangers. A15 is an amberlite of the company Rohm & Haas and SPC118 aproduct of the Bayer company. The polymer rings with the designation ofMPI are described in EP 0 417 407 A1.

The following FIGS. 1 and 2 of the drawing show the macro- and meso-poredistribution of the catalyst according to Experiment 1.

The abbreviations stand for:

in FIG. 1:

V_(Macro) =Volume of the macropores in mL/g measured by mercuryporosimetry

V_(Macro) =Volume of the adsorbed helium in the macropores in mL/g(N.T.P.) measured by helium adsorption

S_(Macro) =Surface of the macropores in m² /g

r_(M) =Average pore radius (in this case that of the macropore)

in FIG. 2:

S_(BET) =Specific surface of the specimen in m² /g measured according tothe BET method

S_(Lec) =Surface based on the standard isotherms according to Lecloux

S_(Meso) =Surface of the mesopores in M² /g

V_(Meso) =Volume of the mesopores

According to IUPAC (1972) the diameters are for:

micropores<2 nm

mesopores 2 nm to 50 nm

macropores>50 nm.

We claim:
 1. Supported catalyst having a shape of a packing, andcomprising an open porous support material having external and internalsurfaces, said external and internal surfaces having affixed thereto amacro-porous ion exchange resin, produced by impregnating or completelycovering the support material with a mixture of (a) polymerizablemonomers for forming the ion exchange resin and (b) at least one of asolvent therefor and a material for forming pores in the ion exchangeresin, and carrying out polymerization.
 2. Supported catalyst accordingto claim 1, produced by a process including an additional step, aftersaid carrying out polymerization, of introducing ion exchange activegroups to polymer product of said polymerization.
 3. Supported catalystaccording to claim 2, obtained by impregnating the support material with0.1 to 60% by weight of a mixture consisting of 10 to 80% by weight ofstyrene, 2 to 25% by weight of divinyl benzene, 1 to 88% by weight of atleast one of the material for forming pores in the ion exchange resinand the solvent and an effective quantity of a polymerization initiatorto initiate polymerization; carrying out the polymerization reactionunder a temperature increase of 30° to 90° C.; and subsequentlysulphonating.
 4. Supported catalyst according to claim 3, wherein themixture impregnating the support material consists of 30-70% by weightstyrene, 5-10% by weight divinyl benzene, 20-50% by weight of at leastone of the material for forming pores in the ion exchange resin and thesolvent, and the effective quantity of the polymerization initiator. 5.Supported catalyst according to claim 2, obtained by adding a mixture of(A) 10 to 80% by weight of styrene, 2 to 25%. by weight of divinylbenzene, 1 to 88% by weight of at least one of the material for formingpores in the ion exchange resin and the solvent, and an effectivequantity of a polymerization initiator to initiate polymerization, and(B) a C₁₄ - to C₁₇ -n-paraffin fraction in a weight ratio of (A):(B) of10:1 to 1:10, to 5 to 50% by weight of the support material, based onthe total mixture, conditioning under vacuum, polymerizing, washing andsubsequently sulphonating.
 6. Supported catalyst according to claim 5,wherein component (A) of the added mixture contains 20-50% by weightstyrene, 5-10% by weight divinyl benzene, 20-50% by weight of said atleast one of the material for forming pores in the ion exchange resinand the solvent, and the effective quantity of the polymerizationinitiator.
 7. Supported catalyst according to claim 3 or 5, wherein themixture polymerized to form the ion exchange resin further comprises afluoro-styrene, a total amount of the styrene and fluoro-styrene beingup to 80% by weight.
 8. Supported catalyst according to any one ofclaims 3, 5, 1 and 2, wherein the material for forming pores in the ionexchange resin is a C₆ to C₁₆ alkane.
 9. Supported catalyst according toany one of claims 3, 5, 1 and 2, wherein the material for forming poresin the ion exchange resin is selected from the group consisting ofn-heptane, pentadecane, i-octane and a mostly C₉ to C₁₃ containingn-paraffin fraction.
 10. Supported catalyst according to claim 5,wherein said washing washes out exposed polymer gel formed during thepolymerization and washes out excess material for forming pores in theion exchange resin.
 11. Supported catalyst according to claim 2 whereinthe ion exchange active groups are introduced by means of exposing theresin to a sulphonating acid.
 12. Supported catalyst according to claim11, wherein said sulphonating acid is selected from the group consistingof aromatic and aliphatic sulphonic acids and sulphuric acid. 13.Supported catalyst according to claim 12, wherein the aromatic sulphonicacid is a benzene sulphonic acid.
 14. Supported catalyst according toclaim 12, wherein the aliphatic sulphonic acid is a methyl sulphonicacid.
 15. Supported catalyst according to claim 11, wherein thesulphonating acid is chlorosulphonic acid.
 16. Supported catalystaccording to claim 2, wherein the polymerizable monomers include vinylmonomers with silane groups, and the catalyst is obtained by reactingmaterial of surfaces of the support material, having OH groups, with thesilane groups as a coupler with surface acidic ion exchange groups beingaffixed by subsequent sulphonation to introduce the ion exchange activegroups.
 17. Supported catalyst according to claim 1 or 2, wherein thesupport material is of sintered glass or sintered glass ceramics, whichhas been contacted with aqueous alkali hydroxide solution prior toimpregnating or completely covering the support material with themixture of polymerizable monomers for forming the ion exchange resin.18. Supported catalyst according to claim 1 or 2, wherein the ionexchange resin is cross-linked to a sufficient degree so that it cannotbe dissolved in a reaction mixture of a reaction to be catalyzed by thesupported catalyst.
 19. Supported catalyst according to claim 1, whereinthe packing is constructed as Raschig rings, Berl saddles, torussaddles, packing rings with web or cross web, Pall rings, hollowspheres, other hollow bodies, ordered packages, or honeycomb bodies,with a proportion of the hollow space of the macro-porous ion exchangeresin being 5 to 95 volume %.
 20. Supported catalyst according to claim1 or 19, treated with Group 7 or Group 8 metals of the periodic table,in quantities of 0.1 to 100 g/kg of the ion exchange resin. 21.Supported catalyst according to claim 20, wherein said Group 7 or Group8 metals is selected from the group consisting of palladium, platinum,ruthenium and rhodium.
 22. Supported catalyst according to claim 1 or19, wherein the support material consists of open-pore glass, sinteredglass, open-pore ceramic material on aluminium silicate base, sinteredglass ceramics, foam ceramics, activated carbon or activated coke. 23.Supported catalyst according to claim 1 or 19, wherein the macro-porousion exchange resin is a macro-porous cross-linked polystyrene sulphonicacid.
 24. Supported catalyst according to claim 1, wherein saidmacro-porous ion exchange resin is affixed chemically to said supportmaterial.
 25. Supported catalyst according to claim 24, wherein thechemical affixing is an affixing achieved by silanising said externaland internal surfaces of the support material, to form silanizedsurfaces, and building up the macro-porous ion exchange resin on thesilanized surfaces.
 26. Supported catalyst according to claim 1 whereinthe solvent is methanol, i-octane, pentadecane or a C₁₄ - to C₁₇-n-paraffin fraction.
 27. Supported catalyst according to claim 1,wherein said macro-porous ion exchange resin is affixed mechanically tosaid support material.
 28. Supported catalyst according to claim 1,wherein the support material is a material different from the ionexchange resin.
 29. Process for carrying out a chemical reaction,comprising introducing chemical reactants into the presence of thesupported catalyst according to claim 1 or 2 and carrying out thechemical reaction, the chemical reaction being at least one selectedfrom the group consisting of etherification, esterification,hydrogenation, dimerization, hydration, alkylization andoligomerization.
 30. Process according to claim 29, wherein,simultaneously with the chemical reaction, a separation operation isperformed.
 31. Process according to claim 30, wherein the separationoperation is selected from the group consisting of adsorption,absorption, extraction, stripping, distillation, rectification,fractionating and membrane separation.
 32. Process according to claim29, wherein the chemical reactants and products of the chemical reactioninclude liquid and gas phases, and wherein the liquid and gas phasesflow in opposite directions to each other.
 33. Process according toclaim 29, wherein the ion exchange resin is sufficiently cross-linkedsuch that the ion exchange resin does not dissolve in the chemicalreactants or products of the chemical reaction.
 34. Process according toclaim 29, wherein the reaction is of alkanols to tertiary alkyl ethers.35. Process according to claim 29, wherein the reaction is of methanoland i-butylene to methyl tertiary butyl ether (MTBE).
 36. Processaccording to claim 29, wherein the reaction is of i-propanol andi-butylene to i-propyl tertiary butyl ether (PBTE).
 37. Processaccording to claim 29, wherein the reaction is of i-butylene and ethanolto ethyl tertiary butyl ether (ETBE).
 38. Process according to claim 29wherein the reaction is of i-pentene-(1) or i-pentene-(2) with methanolto tertiary axyl methyl ether (TAME).
 39. Process according to claim 29,wherein the reaction is of propene and water to i-propanol.
 40. Processaccording to claim 29, wherein the reaction is of i-butylene and waterto tertiary butyl alcohol (TBA).